Siti Mariam Abdul Kadir (2010762233)

Submission Date: 24/12/2013

EXPERIMENT 4: Determination of Avogadro’s number using Electrogravimetry

OBJECTIVE:

To make an experimental measurement of Avogadro’s number using an electrochemical technique

(electrogravimetry).

INTRODUCTION:

The most commonly used basic counting unit chemistry field is Avogadro’s number which was found
by an Italian scientist, Amadeo Avogadro (Vernier Software & Technology, 2013). The definition of
13
Avogadro’s number is the number of atoms in exactly 12 g of the isotope C and the quantity itself is
23
6.02214199 × 10 .

In this experiment, the Avogadro’s number was confirmed by conducting an electrochemical process
called electrolysis. This process used an external power supply to drive and non spontaneous
reaction. A careful measurement of electron flow, amperage, and time to obtain the number of
electrons passing through the electrochemical cell will be done in the experiment. The electron flow,
in amperes, is usually referred to as the current. the Avogadro’s number can be calculated through
the number of atoms in a weighed sample which are related to the number of electrons used.

There are several ways to determine the Avogadro’s number which in this experiment, the
electrogravimetric technique was applied. The experimental setup for this process is called an
electrolytic cell. An electrolytic cell is made up of these following components:

 A direct current source (eg. Battery or power supply)

 Insulated wires to connect the circuit
 Two electrodes
 An electrolyte (sulphuric acid)

The electrolytic process was used to determine the number of electron needed to convert one mole of
2+
copper atoms to one mole of copper ions Cu . This value was divided by to and it represents the
number of atoms converted from copper metal to copper ions:
2+
Cu → Cu 2e

The above reaction is half equation that represents oxidation. The number of copper atoms per mole
of copper is Avogadro’s number, the value to be determined. To find out the number of electron
consumed in this process is determined by using the charge of an electron and the total charge
measured. By using the Millikan oil-drop experiment, the charge of an electron was determined to be
-19
1.60217733 x 10 coulombs per electron.

By applying the relationship: 1 ampere = 1 coulomb/second, the number of coulombs used in this
experiment can be calculated. An ammeter was used in the experiment to measure the amperage
and a stopwatch was used to measure the time passed. The mass of copper that reacted can be
obtained by measuring the mass of the anode and he cathode before and after the electrolysis.

In the electrolytic cell contains both copper electrodes and the electrolyte 1M CuSO4 + 0.5M H2SO4.
The copper electrode (anode) connected to the positive pin loses mass as the copper atoms are
converted into copper ions as shown in the equation earlier. the loss of mass is visible after a while as
2+
pitting of the surface of the metal electrode. In addition, the copper ions, Cu , produced immediately
pass into water solution and deposit on the cathode as the reaction shown below:
2+
Cu 2 e → Cu (solid)
Siti Mariam Abdul Kadir (2010762233)
Submission Date: 24/12/2013

APPARATUS: 20V power supply, U-tube, copper electrodes, electrical wires with crocodile clips,
retort stand with clamps, emery paper and 4-decimal analytical balance.

CHEMICALS: 1M CuSO4 and 0.5M H2SO4

PROCEDURE:

1. Two copper electrodes were obtained, polished and cleaned before any measurement was
taken. The electrodes were dipped in a beaker of clean tap water and then they were dipped
in a beaker of alcohol. a sticker was put to the electrode after the electrode was dried. The
electrodes were weight carefully and less weight electrode was labelled as anode. The
electrolytic solution used was 1M CuSO4 in a 250mL beaker.

2. Based on Figure 1 shown, the circuit was set up by setting the power supply at 20. The
positive pole of the power supply was connected to the anode of the first cell. The cathode
was connected to the positive pin of the ammeter. The amperage was recorded at 30
seconds intervals for 10 minutes. The average amperage was taken to be used in the
calculation.

3. When electrolysis had stopped, the anode and cathode were retrieved, rinsed gently and
dried with distilled water. Then, dried them with tissue paper and immersed in the alcohol. Do
not wipe the electrode since it will remove the copper from the surface. The anode and
cathode were weighted.

4. The same electrodes were used, re-polished with emery paper ad re-weighted. The
electrolysis was repeated using 0.5M H2SO4 solution. The observation at electrode and
electrolyte were recorded.

Figure 1. The circuit set up (Vernier Software & Technology, 2013).

Siti Mariam Abdul Kadir (2010762233)
Submission Date: 24/12/2013

RESULT:

Electrode measurements

CuSO4 H2SO4
Mass of anode before electrolysis 24.9801 g 24.6355 g
Mass of anode after electrolysis 24.1974 g 22.1363 g
Mass loss of anode 0.7827 g 2.4992 g
Mass of cathode before electrolysis 25.3221 g 25.2822 g
Mass of cathode after electrolysis 26.5121 g 28.1709 g
Mass loss of cathode 1.1900 g 2.8887 g
average weight loss at anode 1.6410 g
average weight loss at cathode 2.0394 g

Time-amperage measurements

CuSO4 H2SO4
Time (secs) Current (A) Current (A)
0 0.00 0.00
30 0.98 10.43
60 2.75 10.97
90 3.20 11.51
120 3.60 11.98
150 4.05 12.57
180 4.54 13.12
210 5.07 13.52
240 5.52 13.83
270 5.98 14.00
300 6.38 14.12
330 6.74 14.29
360 7.01 14.47
390 7.20 14.68
420 8.16 14.34
450 8.53 14.44
480 8.77 14.66
510 8.81 14.77
540 8.71 14.76
570 8.61 -
600 8.80 -
Average Current 5.88 12.76
Siti Mariam Abdul Kadir (2010762233)
Submission Date: 24/12/2013

CuSO4 H2SO4
Total time of electrolysis 600 s 540 s
Average current during electrolysis total charge
5.88 12.76
measured (amperes)
Total charge measured (coulombs) 3528 6890 coul
22 22
Number of electrons passed 2.202x10 electrons 4.300x10 electrons
22 2+ 22 2+
Number of Cu2+ generated 1.101x10 Cu ions 2.150x10 Cu ions
Based on weight loss of anode:
21
Number of cu2+ ions/ gram Cu metal (Cu2+/g Cu) 22 8.605x10 Cu
1.407x10 Cu atoms/g
atoms/g
23 23
Avogadro number (from measurement) 8.939 x 10 Cu atoms 5.468x10 Cu atoms
23 23
Avogadro number (true or accepted value) 6.022x10 6.022x10
23 24
Absolute error in measured value 2.919x10 0.554x10
Relative % error in measured value 48.49% 9.20%
Based on weight gain of cathode:
21 21
Number of Cu2+ ions/ gram Cu metal (Cu2+/g 9.2521 x 10 Cu 8.605x10 Cu
Cu) atoms/g atoms/g
23 23
Avogadro number (from measurement) 8.939x10 5.468x10
23 23
Avogadro number (true or accepted value) 6.022x10 6.022x10
23 23
Absolute error in measured value 6.0129 x 10 6.0201 x 10
Relative % error in measured value 48.49% 99.96%

CALCULATIONS:

Electrolysis of copper sulphate with copper Electrolysis of sulphuric acid with copper
electrode: electrode

Anode mass lost: 24.9801 – 24.1974 = 0.7827g Anode mass lost: 24.6333 – 22.1363 = 2.4986g
Current: 5.88A Current: 12.76A
Time of electrolysis: 600s Time of electrolysis: 540s

Total charged passed through the circuit: Total charged passed through the circuit:
= 5.88A x (1 coul/1 amp/s) x 600s = 12.76A x(1 coul/1 amp/s)x540s
= 3528 coul = 6890 coul

Number of electrons: Number of electrons:

-19 -19
=3528 coul x(1 electron/1.6022x10 ) 6890 coul x(1 electron/1.6022x10 )
22 22
=2.202x10 electrons = 4.300x10 electrons

Number of copper atoms lost from the Number of copper atoms lost from the
anode: anode:
22 22
2.202x10 x (1 Cu2+/2 electrons) 4.300x10 x (1 Cu2+/2 electrons)
22 2+ 22 2+
=1.101x10 Cu ions = 2.150x10 Cu ions
Siti Mariam Abdul Kadir (2010762233)
Submission Date: 24/12/2013

Anode

Number of copper ions per gram of Number of copper ions per gram of
copper: copper:
22 2+ 22 2+
1.101x10 Cu ions /0.7827g = 2.150x10 Cu ions/ 2.4986g
22 21
= 1.407x10 Cu atoms/g = 8.605x10 Cu atoms/g

Number of copper atoms in a mole of Number of copper atoms in a mole of

copper, 63.546g/mol copper, 63.546g/mol
22 21
= 1.407x10 Cu atoms/gx63.54g/mol = 8.605x10 Cu atoms/g x 63.54g/mol
23 23
= 8.939x10 = 5.468x10

Percent error:
23 23 Percent error:
Absolute error: 8.939x10 - 6.022x10 = 23 23
23 Absolute error: 5.468x10 - 6.022x10
2.919x10 24
23 = 0.554x10
Percent error: 2.919x10 x 100% 24
23 Percent error: 1.149x10 x 100%
6.022x10 23
6.022x10
= 48.49%
= 9.20%

Cathode

Number of copper ions per gram of

Number of copper ions per gram of
copper:
copper: 22 2+
22 2+ = 2.150 x 10 Cu ions/ 2.8887g
1.101 x 10 Cu ions /1.1900g 21
21 = 7.4427 x 10 Cu atoms/g
= 9.2521 x 10 Cu atoms/g

Number of copper atoms in a mole of Number of copper atoms in a mole of

copper, 63.546g/mol copper, 63.546g/mol
22 21
= 5.7947 x 10 Cu atoms/g x 63.54g/mol = 7.4427 x 10 Cu atoms/g x 63.54g/mol
20 20
= 9.1198 x 10 = 1.1713 x 10

Percent error: Percent error:

20 23 20 23
Absolute error: 9.1198 x 10 - 6.022x10 Absolute error: 1.1713 x 10 - 6.022x10
23 23
= -(6.0129 x 10 ) = -(6.0201 x 10 )
23 24
Percent error: 6.0129 x 10 x 100% Percent error: 1.149x10 x 100%
23 23
6.022x10 6.022x10
= 99.85% = 99.96%
Siti Mariam Abdul Kadir (2010762233)
Submission Date: 24/12/2013

DISCUSSIONS

“Electrogravimetry is electroanalytical method based on gravimetric determination of metallic

elements, which are isolated on the cathode in form of metal or on the anode in form of metal oxide
during electrolysis. This method employs two or three electrodes, and either a constant current or a
constant potential is applied to the preweighed working electrode.“ (University of Wrocław, no date).

The determination of Avogadro’s number was done through electrogravimetric technique. However,
percentage error for each electrolyte was found to be high and nearing 100%. The values were 99.85
% and 99.96 % for CuSO4 and H2SO4 respectively.

Experimentally, the net loss and gain for the Cu ions were found to be higher in H 2SO4 compared to in
CuSO4. It was also found that the cathode thickness in H 2SO4 was found to be thicker compared to
the cathode in CuSO4.This can be justified with the half reactions that took place in H2SO4 is shown
below;
2- - 2-
In H2SO4 :- Anode: S2O8 (aq)+2e → 2SO4 (aq)
+ -
O2 + 4H + 4e → 2H2O
- -
Cathode: 2H2O + 2e → H2(g) + 2OH
2+ -
Cu (aq)+ 2e → Cu (s)
-
At anode, due to the fact that the position of OH in the standard reduction potential (SRP) list is lower
2- - 2-
than the SO4 , therefore, OH was much easier to be discharged compared to SO4 . Whereas at
2+ +
Cu was discharged due to its higher ability to be discharged compared to H .

2+ + 2+
Here, it is clearly shown that the Cu ions needed to compete only with H ions, however Cu ions
2+
would definitely be discharged easily. Higher chances of Cu ions to be reduced caused the
deposition of Cu to be high, say, more efficient. On the other hand, there was a slight difference that
occurred in CuSO4 which can be explained through the half equations as below.
2+ -
In CuSO4 :- Anode: Cu (s) → Cu (aq) + 2e
+ -
O2 + 4H + 4e → 2H2O
- -
Cathode: 2H2O + 2e → H2(g) + 2OH
2+ -
Cu (aq)+2e → Cu(s)

When a very small external current is applied to the copper electrodes, then the equilibrium between
2+
Cu in the solution and the Cu of the electrodes is disturbed. Copper goes into solution at the anode
and an equivalent amount of copper ions are deposited at the cathode (PHYWE, no date).
Theoretically, there is therefore no change in the total amount of dissolved copper sulphate, however,
experiment showed otherwise. The net loss and gain for the electrodes did not tally. The mass loss by
anode was lower compared to the mass gained by the cathode. The possible error was from the
weighing of the electrodes. The electrode must be dried completely before being weighed. The
contribution from electrolyte might have caused the cathode to gain phantom mass.
Siti Mariam Abdul Kadir (2010762233)
Submission Date: 24/12/2013

By referring to the aforementioned justifications in H2SO4, the only difference in CuSO4 was the
reaction took place in the electrolyte that had the same ions as the electrodes used. With this
2+ 2+
situation, the Cu ions from the electrode needed to compete with the Cu from the electrolyte. Thus,
the net gain and loss in this particular electrolyte was lower compared to that of in H 2SO4.

The charge effect efficiency was found to be 58.35% and the calculation is shown as the following:

m = (M x Q)/nF,

where m is the mass of metal deposited, M is the molecular weight, Q (Q= It) is the coulombs, n is the
number of electrons and F is the Faraday’s constant.

At anode, 1.6410g = (63.54 g/mol x Q)/ (2e x 96500 C/mol)

Qa = 3614 C

At cathode, 2.0394g = (63.54 g/mol x Q)/ (2e x 96500 C/mol)

Qc = 6194 C

Charge passed efficiency, Qa/Qc x 100% = 58.35%

Several errors might have occurred in setting up the circuit and experimentally, the presence of
resistance might have reduced the efficiency.

REFERENCES

PHYWE (n.d.) Electrogravimetric determination of copper. Retrieved from:

http://www.phywe.com/index.php/fuseaction/download/lrn_file/versuchsanleitungen/P3062201/e/P306
2201.pdf . [Accessed 22/10/2013].

University of Wrocław. (n.d.) Electrogravimetric Determination Of Copper In Alloys. Faculty of

Chemistry, University of Wrocław, Analytical Chemistry Dept., electrogravimetry. Task 17 - p. 3

Vernier Software & Technology (2013) Determining Avogadro’s Number. Retrieved from:
http://www.vernier.com/experiments/chem-a/31/determining_avogadros_number/ [Accessed
22/10/2013].